Halogen containing dyestuffs of the dibenzanthrone series and process of making same



Patented May 17, 1932 UNITED STATES KARL KRAUER, OF' BASEL, SWITZERLAND,ASSIGNOR TO THE FIRM OF SOCIETY OF 7 PATENTEOFFIICE CHEMICAL INDUSTRY INBASLE, OF BASEL, SWITZERLAND HALOGEN CONTAINING DYESTUFFS OF THEDIBENZANTI-IRONE SERIES AND EBQCESS OF MAKING SAME No Drawing.Application filed October 8, 1931, Serial No; 567,759, and inSwitzerland October 18, 19 30.

"io sulfonic acid on such a dibenzanthrone derivative which contains atleast one w-H group, as being or NH.-

Such derivatives are, for example, the aminodibenzanthrone, thehydroxyolibenzanis throne obtainable therefrom by diazotization andreplacement of the dia-zo-group by the OH-group by boiling, thedihydroxydibenzanthrones obtainable by oxydation of the dibenzanthrone,by fusing the dibenzanthrone Q0 sulfonic acid with caustic alkalies, orby fusing the several hydroxybenzanthrones with caustic alkalies, etc.

The new dyestuffs, the constitution of which is unknown, very probablycontain the dibenzanthrone skeleton P unchanged. They constitute darkpowders which dissolve in sulfuric acid to red-violet to blue solutions,yield with an alkaline hydrosulfite solution red-blue to blue vats, and

dye cotton according tothe natureofthe starting material blue, grey orred-brown tints.

The following examples illustratethe invention, the parts being byweight:

Example 1 parts 'of para-formaldehyde are introduced gradually at 7 080G. into 270 parts of chlorosulphonic acid; dissolution occurs withevolution of hydrogen chloride. Into this solution, at the sametemperature, are introduced 30 parts'of dioxydibenzanthrone of theformula which may be obtained, for example, as described inU. S. PatentNo. 1,093,427, and the Whole is stirred at -80? C. for about 3 hours.After cooling, the solution is poured into ice-water, the violetprecipitate is filtered by suction,washed neutral and dried.

The new chlorinated dyestuff is a blue powder, which dissolves inconcentrated sulfuric acid to a red-violet solution; it yields ared-blue vat and dyes cotton fast blue tints.

into ice-water.

' w being 0 or E wample 2 Into a solution prepared at 80 C. of 50 partsof para-formaldehyde in 270 parts of chlorosulfonic acid there areintroduced 20 parts of aminodibenzanthrone, (the position of theamino-group in the product,

which, as is known, is obtained by nitratingv and reducingdibenzanthrone, is not known) The whole is stirred for3 hours at thesaid temperature, then cooled and introduced The brown precipitate isfiltered, washed and dried.

" Thesolut'ion of the new halogenated dyestuif in sulfuric acid is blueand when diluted with water yields red-brown flocks. The

dye yields a blue vat and dyes cotton redbrown tints which are veryfast.

c What I claimis A manufacture of new dyestuffs ofthe upon thedihydroxydibenzanthrone of the formula I I in presence of chlorosulfonicacid.

3. A manufacture of a new dyestuil' of the dibenzanthrone seriescontaining chlorine, consisting in causing formaldehyde to act uponaminodibenzanthrone, which is obtained by mononitrating'and reducingdibenzanthrone, in presence of 'chlorosulfonic acid. 4. As newproducts'the dyestuffs of the dibenzanthrone series containing chlorine,obtained by causing formaldehyde to act upon such compounds of'thedibenzanthrone series which contain'atileast onew-I-Igroup,

being 0 or NH, in presence of chlor'osulionic acid, which productsdissolve in sulr'u'ric acid to -red-violet to blue solutions, yield withan alkaline hydrosulfite solution red-blue to blue vats, and dye cottonblue, grey to red-brown tints.

5. As a new product the dyestufi of the dibenzanthrone series containingchlorine, obtained by causing formaldehyde to act upon thedihydroxydibenzanthrone of the formula in presence of chlorosulfonic'lacid, which product dissolves in sulfuri c'acid o a redviolet solution,yields 'with 'analkaline sodium hydrosulfi te solution a red-bluevat,"and dyes cotton blue tints. v 1

6. As a new product the dyestuffs of the dis benzanthrone seriescontaining chlorine, obtained by causing formaldehyde to act uponaminodibenzanthrone, which is obtained by mononitrating and reducingdibenzanthrone, 1 100 in presence of chloro'sulfonic acid, which productdissolves in sulfonic acid to a blue solution, yields with an alkalinesodium hy- 1 rosulfite' solution a bluevat, and dyes'cotton red-browntints. a v

r In witness whereof I have hereunto signed my name this 30th day ofSeptember 1931.

KARL AUEB.

